首页 > 最新文献

Journal of the American Chemical Society最新文献

英文 中文
Monooxygenase Activity of Indoleamine 2,3-Dioxygenase. 吲哚胺2,3-双加氧酶的活性。
IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-05 DOI: 10.1021/jacs.5c17552
Ali B Lubis, Anna J Bailey, Marko Hanževački, Christopher Williams, Mehul Jesani, Lola González-Sánchez, Christopher J Arthur, Hannah C Wilson, Andrea E Gallio, Peter C E Moody, Matthew P Crump, Adrian J Mulholland, Allen M Orville, Jonathan Clayden, Emma L Raven

Indoleamine 2,3-dioxygenase (IDO) is a heme-dependent enzyme that catalyzes the first, rate-limiting step of the kynurenine pathway─the oxidation of l-tryptophan to N-formylkynurenine (NFK). IDO-catalyzed depletion of tryptophan levels and accumulation of kynurenine pathway metabolites is an important control mechanism of the immune responses in cells. IDO has been considered as a dioxygenase because two atoms of oxygen are inserted into the substrate. Here, we use LC-MS and NMR to examine the reactivity of human IDO (hIDO) with l-tryptophan (l-Trp) and several other tryptophan analogues. Alongside dioxygenase activity, we identify a concurrent pathway of heme-dependent monooxygenase activity in the reaction of hIDO with l-Trp, leading to the formation of a cyclic 3a-hydroxy-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indole-2-carboxylic acid (HPIC) species. Reaction profiles for the reaction of hIDO with other tryptophan analogues are likewise examined. Formation of HPIC from l-Trp is reproduced in HeLa cells induced to overexpress hIDO, indicating that this dual dioxygenase/monooxygenase reactivity also occurs biologically. Notably, the reaction of hIDO with β-[3-benzo(b)thienyl]-l-alanine (S-l-Trp)─a known inhibitor ─yielded only the cyclic HPIC analogue, suggesting that IDO activity can be selectively directed toward the monooxygenase pathway. Molecular dynamics simulations underscore the critical role of substrate plasticity within the active site of hIDO, while DFT calculations provide a mechanistic rationalization for the observed product distributions. Together, the data demonstrate dual dioxygenase/monooxygenase functionality for human IDO. As the overall gatekeeper for control of tryptophan levels in cells, the findings provide mechanistic information on relevance to therapeutic strategies focused on IDO inhibition.

吲哚胺2,3-双加氧酶(IDO)是一种血红素依赖性酶,催化犬尿氨酸途径的第一个限速步骤─l-色氨酸氧化为n -甲酰基犬尿氨酸(NFK)。ido催化色氨酸水平的消耗和犬尿氨酸途径代谢物的积累是细胞免疫反应的重要控制机制。IDO被认为是一种双加氧酶,因为两个氧原子被插入到底物中。在这里,我们使用LC-MS和NMR来检测人IDO (hIDO)与l-色氨酸(l-Trp)和其他几种色氨酸类似物的反应性。除了双加氧酶活性外,我们还发现了hIDO与l-Trp反应中血红素依赖性单加氧酶活性的同步途径,导致形成环状3-羟基-1,2,3,3a,8,8 - a-六氢吡咯[2,3-b]吲哚-2-羧酸(HPIC)物质。对hIDO与其他色氨酸类似物的反应进行了同样的研究。在诱导过表达hIDO的HeLa细胞中,l-色氨酸形成HPIC,表明这种双加氧酶/单加氧酶反应性也发生在生物学上。值得注意的是,hIDO与已知抑制剂β-[3-苯并(b)噻吩基]-l-丙氨酸(S-l-Trp)的反应仅产生环状HPIC类似物,这表明IDO活性可以选择性地定向于单加氧酶途径。分子动力学模拟强调了基底可塑性在hIDO活性位点中的关键作用,而DFT计算为观察到的产物分布提供了机制上的合理化。总之,这些数据证明了双加氧酶/单加氧酶对人IDO的功能。作为控制细胞中色氨酸水平的整体守门人,研究结果提供了与IDO抑制相关的治疗策略的机制信息。
{"title":"Monooxygenase Activity of Indoleamine 2,3-Dioxygenase.","authors":"Ali B Lubis, Anna J Bailey, Marko Hanževački, Christopher Williams, Mehul Jesani, Lola González-Sánchez, Christopher J Arthur, Hannah C Wilson, Andrea E Gallio, Peter C E Moody, Matthew P Crump, Adrian J Mulholland, Allen M Orville, Jonathan Clayden, Emma L Raven","doi":"10.1021/jacs.5c17552","DOIUrl":"10.1021/jacs.5c17552","url":null,"abstract":"<p><p>Indoleamine 2,3-dioxygenase (IDO) is a heme-dependent enzyme that catalyzes the first, rate-limiting step of the kynurenine pathway─the oxidation of l-tryptophan to <i>N</i>-formylkynurenine (NFK). IDO-catalyzed depletion of tryptophan levels and accumulation of kynurenine pathway metabolites is an important control mechanism of the immune responses in cells. IDO has been considered as a dioxygenase because two atoms of oxygen are inserted into the substrate. Here, we use LC-MS and NMR to examine the reactivity of human IDO (hIDO) with l-tryptophan (l-Trp) and several other tryptophan analogues. Alongside dioxygenase activity, we identify a concurrent pathway of heme-dependent monooxygenase activity in the reaction of hIDO with l-Trp, leading to the formation of a cyclic 3a-hydroxy-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-<i>b</i>]indole-2-carboxylic acid (HPIC) species. Reaction profiles for the reaction of hIDO with other tryptophan analogues are likewise examined. Formation of HPIC from l-Trp is reproduced in HeLa cells induced to overexpress hIDO, indicating that this dual dioxygenase/monooxygenase reactivity also occurs biologically. Notably, the reaction of hIDO with β-[3-benzo(b)thienyl]-l-alanine (S-l-Trp)─a known inhibitor ─yielded only the cyclic HPIC analogue, suggesting that IDO activity can be selectively directed toward the monooxygenase pathway. Molecular dynamics simulations underscore the critical role of substrate plasticity within the active site of hIDO, while DFT calculations provide a mechanistic rationalization for the observed product distributions. Together, the data demonstrate dual dioxygenase/monooxygenase functionality for human IDO. As the overall gatekeeper for control of tryptophan levels in cells, the findings provide mechanistic information on relevance to therapeutic strategies focused on IDO inhibition.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146117140","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Chemoselective 1,2-Sulfonamidoazidation of Styrene via Single-Atom-Site Cobalt Catalysis. 单原子钴催化苯乙烯的1,2-磺酰胺氮化反应。
IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-05 DOI: 10.1021/jacs.5c12264
Wenxuan Xue, Jing Jia, Mingtao Wu, Li-Ming Yang, Rajenahally V Jagadeesh, Matthias Beller, Conghui Tang

Precise control of chemo- and regioselectivity in intermolecular difunctionalization of alkenes remains a long-standing challenge in organic synthesis. Here, we report a heterogeneous cobalt single-atom-site catalyst that enables selective 1,2-sulfonamidoazidation of styrenes. The system features good functional group tolerance and excellent recyclability. By leveraging the characteristics of single-atom-site catalysis, this work provides a valuable platform for achieving highly selective, efficient, and sustainable styrene functionalization.

在烯烃分子间双官能化过程中,精确控制化学选择性和区域选择性一直是有机合成中的一个长期挑战。在这里,我们报道了一种多相钴单原子位催化剂,它可以使苯乙烯选择性地进行1,2-磺酰胺氮化反应。该系统具有良好的官能团容忍度和优良的可回收性。通过利用单原子位点催化的特性,这项工作为实现高选择性、高效和可持续的苯乙烯功能化提供了一个有价值的平台。
{"title":"Chemoselective 1,2-Sulfonamidoazidation of Styrene via Single-Atom-Site Cobalt Catalysis.","authors":"Wenxuan Xue, Jing Jia, Mingtao Wu, Li-Ming Yang, Rajenahally V Jagadeesh, Matthias Beller, Conghui Tang","doi":"10.1021/jacs.5c12264","DOIUrl":"https://doi.org/10.1021/jacs.5c12264","url":null,"abstract":"<p><p>Precise control of chemo- and regioselectivity in intermolecular difunctionalization of alkenes remains a long-standing challenge in organic synthesis. Here, we report a heterogeneous cobalt single-atom-site catalyst that enables selective 1,2-sulfonamidoazidation of styrenes. The system features good functional group tolerance and excellent recyclability. By leveraging the characteristics of single-atom-site catalysis, this work provides a valuable platform for achieving highly selective, efficient, and sustainable styrene functionalization.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146117049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Sculpting Superior Subnanometer Catalysts Directly from Inert Gold 直接从惰性金雕刻优质亚纳米催化剂
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-05 DOI: 10.1021/jacs.5c22389
Ce Liu, Zhaojie Wang, Xiaoqing Lu, Shoufu Cao, Yang-Gang Wang
Bulk gold, renowned for its catalytic inertness, can be transformed into an exceptionally active catalyst by engineering undercoordinated sites on its surface. However, directly sculpting such active sites from extended terraces remains a fundamental challenge. Here, we demonstrate a programmable strategy to dynamically generate subnanometer Au clusters directly from inert Au(111) surfaces, unlocking superior activity for CO oxidation. By integrating large-scale machine learning molecular dynamics with density functional theory, we decode the atomistic pathway of this restructuring process. Our approach employs thermal-CO pressure cycles to induce the ejection of step-edge atoms, forming mobile Au–CO complexes. Subsequent cooling kinetically traps these complexes into metastable, subnanometer clusters (3–6 atoms). A controlled reduction of CO exposure then precisely exposes the catalytically crucial undercoordinated sites while maintaining cluster stability. Crucially, these sculpted clusters exhibit a CO oxidation activity that far exceeds that of pristine step edges, terraces, or conventional single-atom sites. This work establishes reaction condition engineering as a powerful paradigm for sculpting active catalysts directly from bulk materials by bypassing traditional synthetic routes.
大块黄金以其催化惰性而闻名,通过在其表面设计不协调的位点,可以将其转化为特别活跃的催化剂。然而,从扩展的露台上直接雕刻这样的活动场地仍然是一个根本性的挑战。在这里,我们展示了一种可编程策略,可以直接从惰性Au(111)表面动态生成亚纳米级的Au团簇,从而释放出卓越的CO氧化活性。通过将大规模机器学习分子动力学与密度泛函理论相结合,我们解码了这一重组过程的原子路径。我们的方法采用热- co压力循环来诱导台阶边原子的喷射,形成可移动的Au-CO配合物。随后的冷却动力学将这些配合物捕获成亚稳的亚纳米团簇(3-6个原子)。CO暴露的受控减少,然后精确地暴露催化关键的欠协调位点,同时保持簇的稳定性。至关重要的是,这些雕刻团簇表现出的CO氧化活性远远超过了原始台阶边缘,梯田或传统的单原子位置。这项工作建立了反应条件工程作为一个强大的范例,直接从大块材料雕刻活性催化剂,绕过传统的合成路线。
{"title":"Sculpting Superior Subnanometer Catalysts Directly from Inert Gold","authors":"Ce Liu, Zhaojie Wang, Xiaoqing Lu, Shoufu Cao, Yang-Gang Wang","doi":"10.1021/jacs.5c22389","DOIUrl":"https://doi.org/10.1021/jacs.5c22389","url":null,"abstract":"Bulk gold, renowned for its catalytic inertness, can be transformed into an exceptionally active catalyst by engineering undercoordinated sites on its surface. However, directly sculpting such active sites from extended terraces remains a fundamental challenge. Here, we demonstrate a programmable strategy to dynamically generate subnanometer Au clusters directly from inert Au(111) surfaces, unlocking superior activity for CO oxidation. By integrating large-scale machine learning molecular dynamics with density functional theory, we decode the atomistic pathway of this restructuring process. Our approach employs thermal-CO pressure cycles to induce the ejection of step-edge atoms, forming mobile Au–CO complexes. Subsequent cooling kinetically traps these complexes into metastable, subnanometer clusters (3–6 atoms). A controlled reduction of CO exposure then precisely exposes the catalytically crucial undercoordinated sites while maintaining cluster stability. Crucially, these sculpted clusters exhibit a CO oxidation activity that far exceeds that of pristine step edges, terraces, or conventional single-atom sites. This work establishes reaction condition engineering as a powerful paradigm for sculpting active catalysts directly from bulk materials by bypassing traditional synthetic routes.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"89 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122331","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Mesostructured Water Enhances Stability of ProteinMPNN-Designed Ubiquitin-Fold Proteins 介结构水增强蛋白质稳定性:mpnn设计的泛素折叠蛋白
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-05 DOI: 10.1021/jacs.5c19875
Lu-Yi Chen, Wei-Lin Lu, Tanvi Pathania, I-Hsuan Chu, Meng-Ru Ho, Wei-Chen Chuang, Yuan-Chao Lou, Ta I. Hung, Yohei Miyanoiri, Chia-en A. Chang, Kuen-Phon Wu
AI-designed protein variants have demonstrated remarkable resistance to heat and chemical stress, yet the molecular mechanisms underlying this stability remain unclear. Here, we present a comprehensive biophysical and nuclear magnetic resonance (NMR) analysis of thermally stable ubiquitin and its ProteinMPNN-designed variants, R4 and R10, together with a second system based on the less stable ISG15 C-terminal domain (ISG15-CTD). Both R4/R10 and ProteinMPNN-designed ISG15-CTD variants (ICVs) exhibit extraordinary thermostability beyond 120 °C, and resist extreme denaturation at pH 3.0 in 8 M urea. NMR relaxation and hydrogen–deuterium exchange, and molecular-dynamics simulations reveal a protective mesostructured hydration shell that strengthens the hydrogen bonding network between protein-bound and bulk water, thereby suppressing unfolding. Sequence and electrostatic analyses indicate that this hydration arises from charge enrichment and clustering on the protein surface. These findings identify mesostructured hydration as a general, sequence-encoded mechanism of ProteinMPNN-driven stability and provide a physical framework for designing highly resilient biomolecules.
人工智能设计的蛋白质变体已经表现出对热和化学胁迫的显著抗性,但这种稳定性背后的分子机制尚不清楚。在这里,我们对热稳定的泛素及其proteinmpnn设计的变体R4和R10进行了全面的生物物理和核磁共振(NMR)分析,以及基于不太稳定的ISG15 c端结构域(ISG15- ctd)的第二个系统。R4/R10和proteinmpnn设计的ISG15-CTD变体(icv)在120°C以上表现出非凡的热稳定性,并在8 M尿素中抵抗pH 3.0的极端变性。核磁共振弛豫、氢-氘交换和分子动力学模拟揭示了一个保护性的介结构水化壳,它加强了蛋白质结合水和大体积水之间的氢键网络,从而抑制了展开。序列和静电分析表明,这种水合作用是由蛋白质表面的电荷富集和聚集引起的。这些发现确定了介结构水合作用是蛋白质mpnn驱动稳定性的一般序列编码机制,并为设计高弹性生物分子提供了物理框架。
{"title":"Mesostructured Water Enhances Stability of ProteinMPNN-Designed Ubiquitin-Fold Proteins","authors":"Lu-Yi Chen, Wei-Lin Lu, Tanvi Pathania, I-Hsuan Chu, Meng-Ru Ho, Wei-Chen Chuang, Yuan-Chao Lou, Ta I. Hung, Yohei Miyanoiri, Chia-en A. Chang, Kuen-Phon Wu","doi":"10.1021/jacs.5c19875","DOIUrl":"https://doi.org/10.1021/jacs.5c19875","url":null,"abstract":"AI-designed protein variants have demonstrated remarkable resistance to heat and chemical stress, yet the molecular mechanisms underlying this stability remain unclear. Here, we present a comprehensive biophysical and nuclear magnetic resonance (NMR) analysis of thermally stable ubiquitin and its ProteinMPNN-designed variants, R4 and R10, together with a second system based on the less stable ISG15 C-terminal domain (ISG15-CTD). Both R4/R10 and ProteinMPNN-designed ISG15-CTD variants (ICVs) exhibit extraordinary thermostability beyond 120 °C, and resist extreme denaturation at pH 3.0 in 8 M urea. NMR relaxation and hydrogen–deuterium exchange, and molecular-dynamics simulations reveal a protective mesostructured hydration shell that strengthens the hydrogen bonding network between protein-bound and bulk water, thereby suppressing unfolding. Sequence and electrostatic analyses indicate that this hydration arises from charge enrichment and clustering on the protein surface. These findings identify mesostructured hydration as a general, sequence-encoded mechanism of ProteinMPNN-driven stability and provide a physical framework for designing highly resilient biomolecules.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"29 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Caged Ligand-Decorated Near-Infrared Photosensitizer with In Vivo Albumin-Hijacking Capacity for Tumor-Targeted Hypoxia-Tolerant Photoimmunotherapy of Cancer 具有体内白蛋白劫持能力的笼型配体修饰近红外光敏剂用于肿瘤靶向耐缺氧光免疫治疗癌症
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-05 DOI: 10.1021/jacs.5c16988
Xiaofeng Wu, Fan Xing, Yang Yang, Xiaoyang Liu, Gyoungmi Kim, Qiaochu Jiang, Ying Xu, Jing-Jing Hu, Gaolin Liang, Juyoung Yoon
Photoimmunotherapy has been a promising method for eradicating malignant tumors, but remains largely limited by tumor hypoxia and off-target adverse effects. To address these limitations, we develop hypoxia-tolerant small ligand-caged photosensitizer (PS) P1/P2 that are delivered to tumor based on an albumin-hijacking strategy by exploiting endogenous serum albumin as a tumor-localized carrier, achieving exceptional tumor accumulation and overcoming tumor hypoxia to realize the combined photoimmunotherapy. Albumin can trigger the acetyl group of P1/P2, initiating a 1,6-rearrangement elimination cascade to release a quinone methide intermediate captured by albumin to form a stable adduct via site-specific 1,6-Michael addition, as verified by in vitro experiments, including high performance liquid chromatography, mass spectra, spectroscopic spectra, and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) analyses but control probes P3/P4 fail. In vivo imaging revealed that P1/P2 displayed more enhanced tumor accumulation post injection than P3/P4 did in 4T1-bearing mouse models and P1 further enabled broad-spectrum efficacy across several tumor models. Moreover, by light-irradiation-generating superoxide anions and hydroxyl radicals, P1-mediated photodynamic therapy achieves tumor-inhibiting action with approximately 92% regression in a breast mouse model and triggers immunogenic cell death induction, synergizing with programmed death-ligand 1 therapy to further activate systemic antitumor immunity and suppress both primary and distant tumors with approximately 95% tumor growth inhibition. Crucially, this platform may extend its applicability to diverse payloads such as imaging agents, therapeutics, and immunomodulators by replacing the PS warhead and advance delivery methods for clinical imaging and therapy.
光免疫治疗是一种很有前途的根除恶性肿瘤的方法,但仍然很大程度上受到肿瘤缺氧和脱靶副作用的限制。为了解决这些局限性,我们开发了耐缺氧小配体笼型光敏剂(PS) P1/P2,利用内源性血清白蛋白作为肿瘤局部载体,基于白蛋白劫持策略将其递送到肿瘤中,实现异常的肿瘤积累和克服肿瘤缺氧,实现联合光免疫治疗。白蛋白可以触发P1/P2的乙酰基,启动1,6重排消除级联,释放被白蛋白捕获的醌类中间体,通过位点特异性1,6- michael加成形成稳定的加合物,这得到了体外实验的验证,包括高效液相色谱、质谱、光谱和十二烷基硫酸钠-聚丙烯酰胺凝胶电泳(SDS-PAGE)分析,但控制探针P3/P4失败。体内成像显示,在携带4t1的小鼠模型中,P1/P2注射后比P3/P4表现出更强的肿瘤积累,P1进一步在多种肿瘤模型中实现了广谱疗效。此外,通过产生光照射的超氧阴离子和羟基自由基,p1介导的光动力疗法在乳腺小鼠模型中实现了约92%的肿瘤抑制作用,并触发免疫原性细胞死亡诱导,与程序性死亡配体1治疗协同作用,进一步激活全身抗肿瘤免疫,抑制原发和远处肿瘤,约95%的肿瘤生长抑制。至关重要的是,该平台可以通过取代PS弹头和先进的临床成像和治疗递送方法,扩展其适用于不同的有效载荷,如显像剂、治疗剂和免疫调节剂。
{"title":"Caged Ligand-Decorated Near-Infrared Photosensitizer with In Vivo Albumin-Hijacking Capacity for Tumor-Targeted Hypoxia-Tolerant Photoimmunotherapy of Cancer","authors":"Xiaofeng Wu, Fan Xing, Yang Yang, Xiaoyang Liu, Gyoungmi Kim, Qiaochu Jiang, Ying Xu, Jing-Jing Hu, Gaolin Liang, Juyoung Yoon","doi":"10.1021/jacs.5c16988","DOIUrl":"https://doi.org/10.1021/jacs.5c16988","url":null,"abstract":"Photoimmunotherapy has been a promising method for eradicating malignant tumors, but remains largely limited by tumor hypoxia and off-target adverse effects. To address these limitations, we develop hypoxia-tolerant small ligand-caged photosensitizer (PS) <b>P1</b>/<b>P2</b> that are delivered to tumor based on an albumin-hijacking strategy by exploiting endogenous serum albumin as a tumor-localized carrier, achieving exceptional tumor accumulation and overcoming tumor hypoxia to realize the combined photoimmunotherapy. Albumin can trigger the acetyl group of <b>P1</b>/<b>P2</b>, initiating a 1,6-rearrangement elimination cascade to release a quinone methide intermediate captured by albumin to form a stable adduct via site-specific 1,6-Michael addition, as verified by in vitro experiments, including high performance liquid chromatography, mass spectra, spectroscopic spectra, and sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) analyses but control probes <b>P3</b>/<b>P4</b> fail. In vivo imaging revealed that <b>P1</b>/<b>P2</b> displayed more enhanced tumor accumulation post injection than <b>P3</b>/<b>P4</b> did in 4T1-bearing mouse models and <b>P1</b> further enabled broad-spectrum efficacy across several tumor models. Moreover, by light-irradiation-generating superoxide anions and hydroxyl radicals, <b>P1</b>-mediated photodynamic therapy achieves tumor-inhibiting action with approximately 92% regression in a breast mouse model and triggers immunogenic cell death induction, synergizing with programmed death-ligand 1 therapy to further activate systemic antitumor immunity and suppress both primary and distant tumors with approximately 95% tumor growth inhibition. Crucially, this platform may extend its applicability to diverse payloads such as imaging agents, therapeutics, and immunomodulators by replacing the PS warhead and advance delivery methods for clinical imaging and therapy.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"29 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122269","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Production of Subsurface Carbon by Collision Induced Absorption and Its Vibrational Spectroscopic Identification in Au–Ni(111) Au-Ni中碰撞诱导吸收产生亚表面碳及其振动光谱鉴定(111)
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-05 DOI: 10.1021/jacs.5c19883
Santosh K. Singh, Volkan Cinar, S. T. Ceyer
Carbon buried beneath the surface of a metal catalyst has long been suspected to play a key role in graphene and nanotube synthesis, carbon gasification, carbon fuel cells, and Fischer–Tropsch reactions, but the lack of a technique to detect this carbon unambiguously has stymied its definitive identification in that chemistry. This study reports the first vibrational spectroscopic identification of carbon occupying sites beneath a surface, along with its distinction from surface-adsorbed carbon, by the incident energy dependence of its high-resolution electron energy loss intensity. Its assignment is corroborated by its purposeful synthesis via collision-induced absorption, a technique designed to cleanly synthesize bulk carbon by bombardment of surface-bound carbon with 6 eV Xe atoms that pound it beneath the surface. On a Au–Ni(111) surface alloy, subsurface carbon is found to occupy multiple interstitial sites within the dislocation loop below the alloy surface and in Ni octahedral sites, yielding frequencies of 368, 442 and 509, and 694 cm–1, respectively, consistent with previous density functional calculations. Discovery of the spectroscopic signature of bulk carbon provides a handle for its role and/or its reactivity to be explored and ultimately controlled and optimized over that of surface bound carbon in heterogeneous catalytic reactions and materials properties.
长期以来,人们一直怀疑埋在金属催化剂表面下的碳在石墨烯和纳米管合成、碳气化、碳燃料电池和费托反应中起着关键作用,但由于缺乏明确检测这种碳的技术,阻碍了其在化学领域的最终鉴定。这项研究报告了第一个振动光谱识别的碳占据位置下的表面,随着它的区别于表面吸附的碳,通过入射能量依赖的高分辨率电子能量损失强度。碰撞诱导吸收是一种通过6个eV - Xe原子轰击表面结合的碳,将其撞击到表面以下,从而清洁地合成大块碳的技术。在Au-Ni(111)表面合金中,发现亚表面碳占据了合金表面下方位错环内和Ni八面体位置内的多个间隙位置,产生频率分别为368,442和509,以及694 cm-1,与之前的密度泛函计算一致。块状碳的光谱特征的发现为其在非均相催化反应和材料性质中的作用和/或反应性的探索和最终控制和优化提供了一个契机。
{"title":"Production of Subsurface Carbon by Collision Induced Absorption and Its Vibrational Spectroscopic Identification in Au–Ni(111)","authors":"Santosh K. Singh, Volkan Cinar, S. T. Ceyer","doi":"10.1021/jacs.5c19883","DOIUrl":"https://doi.org/10.1021/jacs.5c19883","url":null,"abstract":"Carbon buried beneath the surface of a metal catalyst has long been suspected to play a key role in graphene and nanotube synthesis, carbon gasification, carbon fuel cells, and Fischer–Tropsch reactions, but the lack of a technique to detect this carbon unambiguously has stymied its definitive identification in that chemistry. This study reports the first vibrational spectroscopic identification of carbon occupying sites beneath a surface, along with its distinction from surface-adsorbed carbon, by the incident energy dependence of its high-resolution electron energy loss intensity. Its assignment is corroborated by its purposeful synthesis via collision-induced absorption, a technique designed to cleanly synthesize bulk carbon by bombardment of surface-bound carbon with 6 eV Xe atoms that pound it beneath the surface. On a Au–Ni(111) surface alloy, subsurface carbon is found to occupy multiple interstitial sites within the dislocation loop below the alloy surface and in Ni octahedral sites, yielding frequencies of 368, 442 and 509, and 694 cm<sup>–1</sup>, respectively, consistent with previous density functional calculations. Discovery of the spectroscopic signature of bulk carbon provides a handle for its role and/or its reactivity to be explored and ultimately controlled and optimized over that of surface bound carbon in heterogeneous catalytic reactions and materials properties.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"89 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Topochemical Oxidation of Ruddlesden–Popper Nickelates Reveals Distinct Structural Family: Oxygen-Intercalated Layered Perovskites Ruddlesden-Popper镍酸盐的拓扑化学氧化揭示了独特的结构家族:氧插层状钙钛矿
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-05 DOI: 10.1021/jacs.5c12712
Dan Ferenc Segedin, Jinkwon Kim, Harrison LaBollita, Nicole K. Taylor, Kyeong-Yoon Baek, Suk Hyun Sung, Ari B. Turkiewicz, Grace A. Pan, Abigail Y. Jiang, Maria Bambrick-Santoyo, Tobias Schwaigert, Casey K. Kim, Anirudh Tenneti, Alexander J. Grutter, Shin Muramoto, Alpha T. N’Diaye, Ismail El Baggari, Donald A. Walko, Charles M. Brooks, Antia S. Botana, Darrell G. Schlom, Hua Zhou, Julia A. Mundy
Layered perovskites─including the Dion–Jacobson, Ruddlesden–Popper, and Aurivillius families─exhibit a wide range of correlated electron phenomena, from high-temperature superconductivity to multiferroicity. Here, we report a new family of layered perovskites realized through topochemical oxidation of Lan+1NinO3n+1+δ (n = 1–4) Ruddlesden–Popper nickelate thin films. Postgrowth ozone annealing induces a substantial c-axis expansion─17.8% for La2NiO4+δ (n = 1)─that monotonically decreases with increasing n. Surface synchrotron X-ray diffraction and coherent Bragg rod analysis (COBRA) reveal that this structural expansion arises from the intercalation of approximately δ ≈ 0.7–1.0 oxygen atoms into interstitial sites within the rock salt spacer layers, far exceeding the previous record of δ ≈ 0.3 for any Ruddlesden–Popper oxide. These oxygen-intercalated phases form a new class of layered perovskites with a spacer layer composition intermediate between the Ruddlesden–Popper and Aurivillius phases. Furthermore, oxygen intercalation induces metallicity, enhances nickel–oxygen hybridization, and suppresses oxygen octahedral rotations, a feature associated with high-temperature superconductivity in Ruddlesden–Popper nickelates. Our work establishes topochemical oxidation as a powerful approach to accessing highly oxidized, metastable phases across a broad range of layered oxide systems, offering new platforms to engineer electronic properties via intercalation chemistry.
层状钙钛矿──包括Dion-Jacobson家族、Ruddlesden-Popper家族和Aurivillius家族──表现出从高温超导性到多铁性等广泛的相关电子现象。在这里,我们报告了一个新的层状钙钛矿家族通过拓扑化学氧化的Lan+1NinO3n+1+δ (n = 1 - 4) Ruddlesden-Popper镍酸盐薄膜。生长后臭氧退火诱导了大量的c轴膨胀──La2NiO4+δ (n = 1)的17.8%──随着n的增加而单调降低。表面同步x射线衍射和相干布拉格棒分析(COBRA)表明,这种结构膨胀是由于岩盐间隔层内的间隙位置插入了大约δ≈0.7-1.0个氧原子,远远超过了任何Ruddlesden-Popper氧化物的δ≈0.3的先前记录。这些氧插层相形成了一类新的层状钙钛矿,其间隔层组成介于Ruddlesden-Popper相和Aurivillius相之间。此外,氧嵌入诱导金属丰度,增强镍氧杂化,抑制氧八面体旋转,这是Ruddlesden-Popper镍酸盐中高温超导性的一个特征。我们的工作建立了拓扑化学氧化作为一种强大的方法,可以在广泛的层状氧化物系统中获得高度氧化的亚稳相,为通过插层化学设计电子特性提供了新的平台。
{"title":"Topochemical Oxidation of Ruddlesden–Popper Nickelates Reveals Distinct Structural Family: Oxygen-Intercalated Layered Perovskites","authors":"Dan Ferenc Segedin, Jinkwon Kim, Harrison LaBollita, Nicole K. Taylor, Kyeong-Yoon Baek, Suk Hyun Sung, Ari B. Turkiewicz, Grace A. Pan, Abigail Y. Jiang, Maria Bambrick-Santoyo, Tobias Schwaigert, Casey K. Kim, Anirudh Tenneti, Alexander J. Grutter, Shin Muramoto, Alpha T. N’Diaye, Ismail El Baggari, Donald A. Walko, Charles M. Brooks, Antia S. Botana, Darrell G. Schlom, Hua Zhou, Julia A. Mundy","doi":"10.1021/jacs.5c12712","DOIUrl":"https://doi.org/10.1021/jacs.5c12712","url":null,"abstract":"Layered perovskites─including the Dion–Jacobson, Ruddlesden–Popper, and Aurivillius families─exhibit a wide range of correlated electron phenomena, from high-temperature superconductivity to multiferroicity. Here, we report a new family of layered perovskites realized through topochemical oxidation of La<sub><i>n</i>+1</sub>Ni<sub><i>n</i></sub>O<sub>3<i>n</i>+1+δ</sub> (<i>n</i> = 1–4) Ruddlesden–Popper nickelate thin films. Postgrowth ozone annealing induces a substantial <i>c</i>-axis expansion─17.8% for La<sub>2</sub>NiO<sub>4+δ</sub> (<i>n</i> = 1)─that monotonically decreases with increasing <i>n</i>. Surface synchrotron X-ray diffraction and coherent Bragg rod analysis (COBRA) reveal that this structural expansion arises from the intercalation of approximately δ ≈ 0.7–1.0 oxygen atoms into interstitial sites within the rock salt spacer layers, far exceeding the previous record of δ ≈ 0.3 for any Ruddlesden–Popper oxide. These oxygen-intercalated phases form a new class of layered perovskites with a spacer layer composition intermediate between the Ruddlesden–Popper and Aurivillius phases. Furthermore, oxygen intercalation induces metallicity, enhances nickel–oxygen hybridization, and suppresses oxygen octahedral rotations, a feature associated with high-temperature superconductivity in Ruddlesden–Popper nickelates. Our work establishes topochemical oxidation as a powerful approach to accessing highly oxidized, metastable phases across a broad range of layered oxide systems, offering new platforms to engineer electronic properties via intercalation chemistry.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"12 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122266","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Co-Catalyzed Asymmetric Carbamoyl Radical Addition of Imines 共催化亚胺不对称氨基甲酰自由基加成
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-05 DOI: 10.1021/jacs.5c22992
Wenyu Zhao, Xingyi Shen, Zhaozhao Li, Xuxia Zhang, Aiqi Li, Xianqing Wu, Jingping Qu, Yifeng Chen
Chiral amides are privileged motifs widely found in pharmaceuticals and natural products, spurring the development of robust synthetic methods. While carbamoyl chlorides are convenient and versatile electrophilic precursors, their application in the stereoselective synthesis of sterically hindered amides, particularly those bearing tetrasubstituted stereocenters, remains a formidable challenge. To address this, we have developed a cobalt-catalyzed asymmetric carbamoyl addition to imines, which enables efficient access to structurally demanding α,α-disubstituted α-amino amides under mild conditions with excellent enantioselectivity. Furthermore, this modular strategy facilitates a one-pot cascade to synthesize enantioenriched 2,5-diketopiperazines (DKPs), important scaffolds in medicinal chemistry. Mechanistic studies reveal stereoselective carbamoyl radical addition to forge the chiral C–C bond.
手性酰胺是广泛存在于药物和天然产物中的特殊基序,促进了强大的合成方法的发展。虽然氨甲酰氯是一种方便且用途广泛的亲电前体,但其在立体选择性合成立体受阻酰胺,特别是具有四取代立体中心的酰胺中的应用仍然是一个巨大的挑战。为了解决这个问题,我们开发了一种钴催化的不对称氨甲酰亚胺加成物,它可以在温和的条件下高效地获得结构要求高的α,α-二取代α-氨基酰胺,具有优异的对映选择性。此外,这种模块化策略促进了一锅级联合成对映体富集的2,5-二酮哌嗪(DKPs),这是药物化学中重要的支架。机理研究揭示了立体选择性氨基甲酰自由基加成形成手性C-C键。
{"title":"Co-Catalyzed Asymmetric Carbamoyl Radical Addition of Imines","authors":"Wenyu Zhao, Xingyi Shen, Zhaozhao Li, Xuxia Zhang, Aiqi Li, Xianqing Wu, Jingping Qu, Yifeng Chen","doi":"10.1021/jacs.5c22992","DOIUrl":"https://doi.org/10.1021/jacs.5c22992","url":null,"abstract":"Chiral amides are privileged motifs widely found in pharmaceuticals and natural products, spurring the development of robust synthetic methods. While carbamoyl chlorides are convenient and versatile electrophilic precursors, their application in the stereoselective synthesis of sterically hindered amides, particularly those bearing tetrasubstituted stereocenters, remains a formidable challenge. To address this, we have developed a cobalt-catalyzed asymmetric carbamoyl addition to imines, which enables efficient access to structurally demanding α,α-disubstituted α-amino amides under mild conditions with excellent enantioselectivity. Furthermore, this modular strategy facilitates a one-pot cascade to synthesize enantioenriched 2,5-diketopiperazines (DKPs), important scaffolds in medicinal chemistry. Mechanistic studies reveal stereoselective carbamoyl radical addition to forge the chiral C–C bond.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"9 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122332","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Low-Dimensional Zeotypes Templated by Stacked Cyclic Benzimidazolium Revealed by Electron Crystallography. 叠叠环苯并咪唑模板化低维Zeotypes的电子晶体研究。
IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-05 DOI: 10.1021/jacs.5c22569
Evgeniia Ikonnikova, Jung Cho, Xiaodong Zou, Andre Sutrisno, Allen W Burton, Trong Pham, Tom Willhammar

The structural diversity of zeolites depends strongly on the use of organic structure-directing agents (OSDAs) that guide their formation. Low-dimensional zeolitic materials, such as layered or chain-like phases, can serve as key intermediates in topotactic condensation pathways, yet the mechanisms governing their formation and transformation remain poorly understood. Here, we report three low-dimensional zeolitic materials, EMM-75P, EM-L01, and EM-L02, synthesized using benzimidazolium cations as OSDAs. Their structures were determined by three-dimensional electron diffraction (3D ED), including the atomic structure of the OSDAs, revealing their confinement within the framework to shed light on their structure-directing role. The bulky benzimidazolium OSDAs prevent the formation of materials with three-dimensional framework structures and instead direct the formation of low-dimensional zeotypes. Upon calcination, the two-dimensional layered aluminosilicate zeotype EMM-75P undergoes topotactic condensation to form a three-dimensional zeolite, EMM-75, with a previously unreported zeolite framework topology. Aluminosilicate EM-L01 is a 2D analogue of STF/SFF zeolite frameworks and partially condensed to an STF-topology upon calcination, whereas EM-L02, a 1D silicate composed of double 6-ring chains, packed analogous to the CHA zeolite framework, collapses during the thermal treatment. The detailed structural characterization of these three materials provides insights into the mechanism of topotactic condensation and demonstrates how such pathways can lead to new zeolite materials.

沸石的结构多样性在很大程度上取决于有机结构导向剂(OSDAs)的使用,以指导它们的形成。低维沸石材料,如层状或链状相,可以作为拓扑凝聚途径的关键中间体,但控制其形成和转化的机制仍然知之甚少。本文报道了三种低维沸石材料EMM-75P, EM-L01和EM-L02,以苯并咪唑阳离子为osda合成。通过三维电子衍射(3D ED)确定了它们的结构,包括osda的原子结构,揭示了它们在框架内的限制,从而阐明了它们的结构指导作用。体积庞大的苯并咪唑osda阻止了具有三维框架结构的材料的形成,而是指导了低维零型的形成。在煅烧后,二维层状铝硅酸盐分子筛EMM-75P经过拓扑凝聚形成三维分子筛EMM-75,具有以前未报道的分子筛框架拓扑结构。铝硅酸盐EM-L01是STF/SFF分子筛框架的二维类似物,在煅烧时部分凝聚成STF拓扑结构,而EM-L02是由双6环链组成的一维硅酸盐,与CHA分子筛框架类似,在热处理过程中坍塌。这三种材料的详细结构表征提供了对拓扑凝聚机制的见解,并展示了这种途径如何导致新的沸石材料。
{"title":"Low-Dimensional Zeotypes Templated by Stacked Cyclic Benzimidazolium Revealed by Electron Crystallography.","authors":"Evgeniia Ikonnikova, Jung Cho, Xiaodong Zou, Andre Sutrisno, Allen W Burton, Trong Pham, Tom Willhammar","doi":"10.1021/jacs.5c22569","DOIUrl":"https://doi.org/10.1021/jacs.5c22569","url":null,"abstract":"<p><p>The structural diversity of zeolites depends strongly on the use of organic structure-directing agents (OSDAs) that guide their formation. Low-dimensional zeolitic materials, such as layered or chain-like phases, can serve as key intermediates in topotactic condensation pathways, yet the mechanisms governing their formation and transformation remain poorly understood. Here, we report three low-dimensional zeolitic materials, EMM-75P, EM-L01, and EM-L02, synthesized using benzimidazolium cations as OSDAs. Their structures were determined by three-dimensional electron diffraction (3D ED), including the atomic structure of the OSDAs, revealing their confinement within the framework to shed light on their structure-directing role. The bulky benzimidazolium OSDAs prevent the formation of materials with three-dimensional framework structures and instead direct the formation of low-dimensional zeotypes. Upon calcination, the two-dimensional layered aluminosilicate zeotype EMM-75P undergoes topotactic condensation to form a three-dimensional zeolite, EMM-75, with a previously unreported zeolite framework topology. Aluminosilicate EM-L01 is a 2D analogue of <b>STF</b>/<b>SFF</b> zeolite frameworks and partially condensed to an <b>STF</b>-topology upon calcination, whereas EM-L02, a 1D silicate composed of double 6-ring chains, packed analogous to the <b>CHA</b> zeolite framework, collapses during the thermal treatment. The detailed structural characterization of these three materials provides insights into the mechanism of topotactic condensation and demonstrates how such pathways can lead to new zeolite materials.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146123259","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Shifting Merocyanine-Imine Exchange with Visible Light 可见光下移动的merocyanine -亚胺交换
IF 15 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-05 DOI: 10.1021/jacs.5c17606
Alwin Drichel, Stefan Hecht
We show the dynamic covalent exchange between merocyanines and imines and demonstrate how the equilibrium composition can be shifted with visible light. For this purpose, we exploited a negative photochromic T-type merocyanine that engages in a covalent exchange with an aniline nucleophile to provide an imine. Since the merocyanine can quantitatively be converted into its spiropyran isomer that is nonreactive in the exchange, the system can be shifted and trapped in the static spiropyran state. In the dark, however, the system thermally reverts back to the dynamic merocyanine that re-engages in the exchange. The process of shifting/trapping and re-equilibration can be repeated multiple times. The system provides opportunities for designing materials that allow for spatial and temporal control over their dynamic properties.
我们展示了merocyanines和亚胺之间的动态共价交换,并演示了平衡组成如何在可见光下转移。为此,我们利用负光致变色t型merocyanine与苯胺亲核试剂进行共价交换,生成亚胺。由于merocyanine可以在交换中定量地转化为螺吡喃异构体,而螺吡喃异构体在交换中没有反应性,因此该体系可以移位并被困在静态螺吡喃状态。然而,在黑暗中,系统热恢复到动态的merocyanine,重新参与交换。移动/捕获和重新平衡的过程可以重复多次。该系统为设计材料提供了机会,允许对其动态特性进行空间和时间控制。
{"title":"Shifting Merocyanine-Imine Exchange with Visible Light","authors":"Alwin Drichel, Stefan Hecht","doi":"10.1021/jacs.5c17606","DOIUrl":"https://doi.org/10.1021/jacs.5c17606","url":null,"abstract":"We show the dynamic covalent exchange between merocyanines and imines and demonstrate how the equilibrium composition can be shifted with visible light. For this purpose, we exploited a negative photochromic T-type merocyanine that engages in a covalent exchange with an aniline nucleophile to provide an imine. Since the merocyanine can quantitatively be converted into its spiropyran isomer that is nonreactive in the exchange, the system can be shifted and trapped in the static spiropyran state. In the dark, however, the system thermally reverts back to the dynamic merocyanine that re-engages in the exchange. The process of shifting/trapping and re-equilibration can be repeated multiple times. The system provides opportunities for designing materials that allow for spatial and temporal control over their dynamic properties.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"89 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122297","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
期刊
Journal of the American Chemical Society
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1